Spiro-oxazine compound

ABSTRACT

A spiro-oxazine compound represented by the following general formula (A) or (A&#39;) is a photochromic compound having an excellent fatigue resistance to repetition of coloration and decoloration and an abundance of hues: ##STR1## wherein the α ring is a ring selected from a 5-membered ring having one N atom, which may be connected to a benzene ring or naphthalene ring, and a 6-membered ring having one N atom, with the proviso that the N atom in the αring is bonded to a C 1-20  alkyl or another organic group, X is selected from O, S, Se and N--R 1  (in which R 1  is selected from H, and C 1-20  alkyl and other organic groups), R 2  and R 3  are selected from --OH, amino, C 1-20  alkoxy, halogen, and other groups, and k is an integer of 0 to 2.

This application is a continuation of application Ser. No. 07/425,205filed on Oct. 6,1989, now abandoned.

TECHNICAL FIELD

The present invention relates to a spiro-oxazine compound. Moreparticularly, the present invention relates to a photochromic compoundvaluable as a printing material, an optical recording material, arecording material, a clothing material, a decorating material and thelike.

BACKGROUND ART

A spiropyran compound can be mentioned as a typical photochromiccompound, and many photochromic spiropyran compounds are known [G. H.Brown, "Photochromism", Wiley Interscience, New York (1971)].

Spiropyran compounds, however, have a problem of poor fatigue resistanceat the repetition of coloration and decoloration.

A spiro-oxazine compound is known as a photochromic compound having animproved fatigue resistance. For example, Japanese Unexamined PatentPublication No. 62-205185 discloses the following compound: ##STR2##

However, In the conventional spiro-oxazine compounds, however, the hueof the chromophoric seed is limited to violet-to-blue, and thus theyhave a low selection of hues.

DISCLOSURE OF THE INVENTION

The present invention is intended to overcome the above-mentioneddefects of the conventional technique, and an object of the presentinvention is to provide a photochromic compound having an excellentfatigue resistance upon a repetition of coloration and decoloration andan abundance of hues.

According to the present invention, the above-mentioned object isobtained by providing a spiro-oxazine compound represented by thefollowing general formula (A) or (A'): ##STR3## wherein the e ring is aring selected from the group consisting of a 5-membered ring having onenitrogen atom, a 5-membered ring having one nitrogen atom and connectedto a benzene ring or naphthalene ring and a 6-membered ring having onenitrogen atom, with the proviso that the nitrogen atom in the α ring isbonded to an organic group R⁰ as expressed as >N--R⁰ (in which R⁰ standsfor a substituent selected from the group consisting of an alkyl grouphaving 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbonatoms, an aralkyl group having 7 to 20 carbon atoms and an aryl grouphaving 6 to 19 carbon atoms); the β ring is a benzene ring or anaphthalene ring, X stands for one member selected from the groupconsisting of O, S, Se and N--R¹ (in which R¹ stands for one memberselected from the group consisting of a hydrogen atom, an alkyl grouphaving 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbonatoms, an aralkyl group having 7 to 20 carbon atoms, an aryl grouphaving 6 to 19 carbon atoms and an acyl group having 2 to 20 carbonatoms); R² and R³ stand for a substituent selected from the groupconsisting of a hydroxyl group, an amino group, an alkoxy group having 1to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, anaryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenylgroup having 2 to 20 carbon atoms, an aralkyl group having 7 to 15carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogengroup, a cyano group, a carboxyl group, a nitro group (not included inR³), an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl grouphaving 2 to 20 carbon atoms, a carbamoyl group, a carbamoyloxy group anda sulfonic acid group (not included in R³), with the proviso that ahydrogen atom is included in R³ ; and k is an integer of from 0 to 2.

BEST MODE FOR CARRYING OUT THE INVENTION

In the compound of the present invention represented by the generalformula (A) or (A'), the α ring is a 5-membered or 6-membered ringhaving one nitrogen atom, or a 5-membered ring having one nitrogen atomand connected to a benzene ring or naphthalene ring. As specificexamples, there can be mentioned a pyrrolidine ring, a pyrrole ring, apiperidine ring, a tetrahydropyridine ring, a dihydropyridine ring, anindoline ring, and a benzindoline ring.

The nitrogen atom contained in the α ring is bonded to an organic groupR⁰ as expressed as >N--R⁰.

As specific examples of the substituent R⁰, there can be mentionedlinear alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyland octadecyl groups, branched alkyl groups having 3 to 20 carbon atoms,such as tert-butyl and 2-methylpentyl groups, cycloalkyl groups having 3to 10 carbon atoms, such as cyclohexyl, norbornyl and adamantyl groups,alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl,hexenyl, 1,3-butadienyl and isopropenyl groups, aralkyl groups having 7to 20 carbon atoms, such as benzyl, phenethyl and (2-naphthyl)methylgroups, and aryl groups having 6 to 19 carbon atoms, such as phenyl and2-naphthyl groups. R⁰ may be substituted. As specific examples of thesubstituent for R⁰ there can be mentioned a hydroxyl group, amino groupssuch as amino, dibenzylamino and (2-methacryloxyethyl)amino groups,alkoxy groups such as methoxy, ethoxy and propoxy groups, acyloxy groupssuch as acetoxy, benzoyloxy, acryloxy and methacryloxy groups, alkylgroups such as methyl, ethyl, trifluoromethyl and butyl groups, aralkylgroups such as benzyl and 4-(2,3-epoxypropyl)phenethyl groups, arylgroups such as phenyl and styryl groups, halogen groups such as fluoroand chloro groups, a cyano group, a carboxyl group, a nitro group, anacetyl group, acyl groups such as acetyl and methylacryl groups,alkoxycarbonyl groups such as ethoxycarbonyl and3,4-epoxybutyloxycarbonyl groups, carbamoyl groups such as carbamoyl,N-phenylcarbamoyl and N-(2-methacryloxy)ethylcarbamoyl groups,carbamoyloxy groups such as an [N-(acryloxy)propylcarbamoyl]oxy group,and sulfonic acid groups such as a sulfonic acid group and metal saltsthereof (for example, sodium and lithium salts).

The β ring, which is included in the general formula (A) or (A') as wellas the α ring, is a benzene ring or a naphthalene ring.

Other constituents included in the general formula (A) or (A') will nowbe described.

X is one member selected from the group consisting of O, S, Se andN--R¹, in which R¹ stands for one member selected from the groupconsisting of a hydrogen atom, an alkyl group having 1 to 20 carbonatoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl grouphaving 7 to 20 carbon atoms, an aryl group having 6 to 19 carbon atomsand an acyl group having 2 to 20 carbon atoms. R¹ may be substituted. Asspecific examples of the alkyl, alkenyl, aralkyl and aryl groups as R¹,inclusive of substituents contained in R¹, there can be mentioned thoseexemplified above with respect to R⁰, and as the acyl group, there canbe mentioned an acetyl group and a methacryl group.

In order to obtain a compound having an excellent repetition durabilityand having a plurality of absorption bands of the chromophoric seed, Xis preferably O. Furthermore, to obtain a chromophoric seed of a brightred hue, X is preferably N--R¹.

As specific examples of R² and R³, there can be mentioned a hydroxylgroup, substituted and unsubstituted amino groups such as amino,dimethylamino, dibenzylamino and (2-methacryloxyethyl)amino groups,alkoxy groups having 1 to 20 carbon atoms, such as methoxy, ethoxy,propoxy and butoxy groups, aralkoxy groups having 7 to 15 carbon atoms,such as benzyloxy and phenethyloxy groups, aryloxy groups having 6 to 14carbon atoms, such as phenoxy and naphthyloxy groups, acyloxy groupshaving 2 to 20 carbon atoms, such as benzoyloxy, acryloxy andmethacryloxy groups, alkyl groups having 1 to 20 carbon atoms, such asmethyl, ethyl, propyl, butyl, tert-butyl, glycidyl and octadecyl groups,alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl,isopropenyl, 1,3-butadienyl and 9,12-octadecadienyl groups, aralkylgroups having 7 to 15 carbon atoms, such as benzyl, phenetyl andnaphthylmethyl groups, aryl groups having 6 to 14 carbon atoms, such asphenyl and naphthyl groups, halogen groups such as chloro, fluoro andbromo groups, a cyano group, a carboxyl group, a nitro group (notincluded in R³), acyl groups having 2 to 20 carbon atoms, such asacetyl, methacryl and acryl groups, alkoxycarbonyl groups having 2 to 20carbon atoms, such as ethoxycarbonyl and 3,4-epoxybutyloxycarbonylgroups, unsubstituted and substituted carbamoyl groups such ascarbamoyl, N-phenylcarbamoyl and N-(2-methacryloxy)ethylcarbamoylgroups, carbamoyloxy groups such as [N-(3-acryloxy)propylcarbamoyl]oxyand [N-(methacryloxy)propylcarbamoyl]oxy groups, and sulfonic acidgroups (not included in R³) such as a sulfonic acid group and metalsalts thereof (for example, sodium and lithium salts). Furthermore, ahydrogen atom is included in R³.

Note, k is an integer of from 0 to 2, and where k is 2, two R² groupsmay be the same or different.

As specific examples of the spiro-oxazine compound of the presentinvention represented by the general formula (A) or (A'), there can bementioned the following compounds.

(a) Spiro-oxazine compounds represented by the following general formula(B) or (B'): ##STR4## wherein R⁰, R², R³, X and k are as defined in thegeneral formula (A) or (A'), R⁴ and R⁵ independently stand for asubstituent selected from the group consisting of an alkyl group having1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms andan aryl group having 6 to 19 carbon atoms, or R⁴ and R⁵ together form acycloalkyl group having 3 to 10 carbon atoms with the carbon atom at the3-position, R⁶ and R⁷ stand for a substituent selected from the groupconsisting of a hydroxyl group, an amino group, an alkoxy group having 1to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, anaryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenylgroup having 2 to 20 carbon atoms, an aralkyl group having 7 to 15carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogengroup, a cyano group, a carboxyl group, a nitro group, an acyl grouphaving 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20carbon atoms, a carbamoyl group, a carbamoyloxy group and a sulfonicacid group, and l and m stand for an integer of from 0 to 4.

(b) Spiro-oxazine compounds represented by the following general formula(C) or (C'): ##STR5## wherein R⁰, R², R³, X and k are as defined in thegeneral formula (A) or (A'), R⁴, R⁵, R⁶, R⁷, l and m are as defined inthe general formula (B) or (B'), R⁸ stands for a substituent selectedfrom the group consisting of a hydroxyl group, an amino group, an alkoxygroup having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxygroup having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbonatoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl grouphaving 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms,a halogen atom, a cyano group, a carboxyl group, a nitro group, an acylgroup having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to20 carbon atoms, a carbamoyl group, a carbamoyloxy group and a sulfonicacid group, and n is an integer of from 0 to 2.

(c) Spiro-oxazine compounds represented by the following general formula(D) or (D'): ##STR6## wherein R⁰, R², R³, X and k are as defined in thegeneral formula (A) or (A'), R⁴, R⁵, R⁶, R⁷, l and m are as defined inthe general formula (B) or (B'), and R⁸ and n are as defined in thegeneral formula (C) or (C').

(d) Spiro-oxazine compounds represented by the following general formula(E) or (E'): ##STR7## wherein R⁰, R², R³, X and k are as defined in thegeneral formula (A) or (A'), R⁴ R⁵, R⁶, and l are as defined in thegeneral formula (B) or (B'), and R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ standfor one member selected from the group consisting of a hydrogen atom, analkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20carbon atoms and an aryl group having 6 to 19 carbon atoms.

(e) Spiro-oxazine compounds represented by the general formula (F) or(F'): ##STR8## wherein R⁰, R², R³, X and k are as defined in the generalformula (A) or (A') R⁴, R⁵, R⁶, R⁷, l and m are as defined in thegeneral formula (B) or (B'), R¹⁵ stands for a substituent selected fromthe group consisting of a hydroxyl group, an amino group, an alkoxygroup having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxygroup having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbonatoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl grouphaving 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms,a halogen atom, a cyano group, a carboxyl group, a nitro group, analkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group, acarbamoyloxy group and a sulfonic acid group, and t is an integer offrom 0 to 2. In the spiro-oxazine compounds represented by theabove-mentioned general formulae (B), (B'), (C), (C'), (D) and (D'), asspecific examples of R⁴ and R⁵ which are independent from each other,there can be mentioned linear alkyl groups having 1 to 20 carbon atoms,such as methyl, ethyl and octadecyl groups, branched alkyl groups having3 to 20 carbon atoms, such as a 2-methylpentyl group, cycloalkyl groupshaving 3 to 10 carbon atoms, such as a cyclohexyl group, aralkyl groupshaving 7 to 20 carbon atoms, such as benzyl and phenethyl groups andaryl groups having 6 to 19 carbon atoms, such as a phenyl group, and asspecific examples of the group formed by combined R⁴ and R⁵ togetherwith the carbon at the 3-position, there can be mentioned cycloalkylgroups having 3 to 10 carbon atoms, such as cyclohexyl, norbornyl andadamantyl groups.

R⁴ and R⁵ may be substituted. As the substituent for R⁴ and R⁵, therecan be mentioned those exemplified above as the substituent for R⁰.

R⁶, R⁷ and R⁸ are as defined in the general formula (A) or (A') withrespect to R². l, m and n are as defined above, and if they are 2 ormore, two or more of corresponding R⁶, R⁷ or R⁸ groups may be the sameor different.

In the spiro-oxazine compounds represented by the above-mentionedgeneral formula (E) or (E'), R⁰, R², R³, R⁴, R⁵, R⁶, X, k and l are asdefined in the above-mentioned general formulae (A), (A'), (B), (B')(C), (C') (D) and (D'), and R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ are selectedfrom the group consisting of a hydrogen atom and the same alkyl, aralkyland aryl groups as exemplified above with respect to R² in the generalformula (A) or (A'). All of these groups may be the same or different.

In the spiro-oxazine compounds represented by the general formula (F) or(F'), groups other than R¹⁵ are as mentioned in the other generalformulae, and R¹⁵ is selected from groups exemplified above with respectto R⁰ in the general formula (A) or (A'). If t is 2, two R¹⁵ groups maybe the same or different.

As is apparent from the foregoing description, the spiro-oxazinecompound of the present invention is characterized in that thespiro-oxazine compound comprises not only the above-mentioned α ring butalso an oxazine ring, a benzene ring, a heterocyclic 5-membered ring andthe β ring. Especially, a compound in which the benzene ring,heterocyclic 5-membered ring and β ring are consecutively by connected,R³ is a hydrogen atom and X is O, S or Se, has absorption peaks in bothof the short wavelength region (less than 550 nm) and long wavelengthregion (more than 600 nm) of the visible ray region, and even a compounddeveloping a green color can be obtained. Furthermore, if R³ has asubstituent other than hydrogen or X is N--R¹, a compound developing ared color can be obtained. Accordingly, the spiro-oxazine compound ofthe present invention has an abundance of chromophoric seed. Moreover,the spiro-oxazine compound of the present invention has an excellentfatigue resistance to the repetition of coloration and decoloration.

The general formulae (A) and (A') in the present invention are isomericto each other, and an appropriate isomer is selected according to theintended object in view of the kinds of substituents and the desiredphotochromic characteristics.

The compound of the present invention represented by the formula (A) or(A') is prepared, for example, according to the following processes.

According to the first process, a methylene compound represented by thefollowing general formula (I): ##STR9## is reacted with a nitrosocompound represented by the following general formula (II) or (II'):##STR10## to prepare a compound represented by the formula (A) or (A').

According to the second process, a compound represented by the followinggeneral formula (III):

     α C--CH.sub.2 R.sup.3

is reacted with a quaternarizing agent R⁰ --Y (Y stands for an anionicleaving group), a basic substance and a compound represented by thegeneral formula (II) or (II') in an optional order to obtain a compoundrepresented by the formula (A) or (A').

According to the third process, a reaction product between a compoundrepresented by the formula (I) and nitrous acid is reacted with an aminocompound represented by the following general formula (IV) or (IV'):##STR11## to prepare a compound represented by the formula (A) or (A').

According to the fourth process, a reaction product between a compoundrepresented by the formula (III) and nitrous acid is reacted with aquaternarizing agent R⁰ --Y, a basic substance and a compoundrepresented by the general formula (IV) or (IV') in an optional order toprepare a compound represented by the formula (A) or (A').

According to the fifth process, a reaction product between a compoundrepresented by the following general formula (V): ##STR12## and nitrousacid is reacted with a basic substance and a compound represented by thegeneral formula (IV) or (IV') in an optional order to prepare a compoundrepresented by the formula (A) or (A').

As the purification method in the preparation process, preferablyrecrystallization using various solvents, column chromatographyseparation using a silica column or the like, solvent extraction andactive carbon treatment are adopted.

The spiro-oxazine compound of the present invention is preferably usedin combination with an optically transparent resin. As the resin, therecan be mentioned, for example, a diethylene glycol bis-allylcarbonatepolymer, a (meth)acrylic polymer, a copolymer thereof, a cellulose,polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, a polyesterresin, polycarbonate, polystyrene, a copolymer thereof, an epoxy resin,a (halogenated) bisphenol A di(meth)acrylate polymer, a copolymerthereof, a (halogenated) bisphenol A urethane-modified di(meth)acrylatepolymer, a copolymer thereof, a nylon resin and polyurethane.

If the spiro-oxazine compound of the present invention has an alkenylgroup, that is, a polymerizable functional group such as a methacryloxygroup or a vinyl group, by copolymerization of this spiro-oxazinecompound with other polymerizable compound such as an acrylic monomer, astyrene type monomer or a vinyl acetate type monomer, the spiro-oxazinecompound can be integrated with a polymer resin of the otherpolymerizable compound. If the spiro-oxazine compound is thus integratedby the copolymerization, a preferred photochromic material having anexcellent durability of the spiro-oxazine compound can be obtained.

Compounds of the general formulae (A) through (F) and (A') through (F')having polymerizable functional groups at R⁰, R², R⁶, R⁷ and R¹⁵ arepreferable from the viewpoint of the durability. Compounds having apolymerizable functional group at R⁰, which is introduced through amethylene chain having at least 3 carbon atoms, are especiallypreferred. A methacryloxy group is especially preferred as thepolymerizable functional group, because the radical polymerization iseasily accomplished and decomposition is prevented during thepolymerization.

If the compound of the present invention has a polymerizable functionalgroup, the compound can be used in the form of not only a copolymer asmentioned above but also a homopolymer.

The photochromic compound of the present invention can be preferablyused as an optical element having photochromic characteristics in theform of a combination with a resin, a polymer of the compound or acombination of this polymer with other resin. As the optical element,there can be mentioned sunglass lens, ski goggles and protective glasslens. Furthermore, the photochromic compound of the present inventioncan be preferably used for curtaining, clothing, automobile windows suchas a front glass or sun roof, toys, toilet articles and writing tools.

As the method for combining the photochromic compound of the presentinvention, various methods can be adopted, for example, a dyeing method,a casting method and a polymer solution-coating method. Instead of thepolymer solution-coating method, a method can be adopted in which anemulsion is formed and the emulsion is coated by screen printing.Moreover, various printing methods, for example, a gravure printingmethod, can be adopted. As the coating method, various coating methodscan be adopted, such as a dip coating method, a spin coating method anda roll coating method.

In many cases, the chromophoric seed of the compound of the presentinvention has at least two absorption peaks, and therefore, the compoundof the present invention is valuable as a material for a rewritableoptical disk.

The amount of the compound of the present invention to be combined withthe resin should be determined according to the object and theapplication method, but from the view, point of visual sensitivity,preferably the amount of the compound of the present invention is 0.01to 20% by weight based on the resin.

To improve the repetition durability of the photochromic compound of thepresent invention, preferably oxygen and water are intercepted when thecompound of the present invention is used. Furthermore, known additivescan be used to further improve the durability. For example, there can beused a single t oxygen quencher represented by a nickel salt, anantioxidant represented by a hindered amine or a polymer thereof and anultraviolet absorber having no influence on the photochromiccharacteristics.

The present invention will now be described in detail with reference tothe following examples that by no means limit the scope of theinvention.

EXAMPLE 1

(1) Synthesis of 1-nitroso-2-hydroxydibenzofuran

In 100 g of pyridine was dissolved 10 g of 2-hydroxydibenzofuran, andthe solution was cooled to 0° C. Then, 60 g of a 20% aqueous solution ofsodium nitrite was added to the above solution and 100 g of a 30%aqueous solution of sulfuric acid was added dropwise to the mixturewhile stirring for 10 minutes. After the dropwise addition, the mixturewas stirred at 0° C. for 1 hour and then filtered. The recovered solidwas washed with water and dried to obtain 11 g of a red crystal of1-nitroso-2-hydroxydibenzofuran.

(2) Results of analysis

Elementary analysis values:

    ______________________________________                                        Found Value (%)  Calculated Value (%)                                         ______________________________________                                        C       67.7         67.7                                                     H       3.2          3.3                                                      N       6.3          6.6                                                      ______________________________________                                    

NMR (protons other than OH): 6.7 ppm (d, 1H), 7.4 ppm (t, 1H), 7.5 ppm(t, 1H), 7.6 ppm (d, 1H), 7.7 ppm (d, 1H), 8.3 ppm (d, 1H)

(3) Synthesis of spiro-oxazine of following formula (G): ##STR13##

In 100 ml of absolute ethanol were dissolved 10 g of1,3,3-trimethyl-2-methylene-indoline and 10 g of1-nitroso-2-hydroxydibenzofuran, and reaction was carried out at thereflux temperature for 1 hour. After the reaction, the reaction mixturewas concentrated and subjected to column chromatography separation usingsilica gel as the supporting carrier and methylene chloride as thedeveloping solvent. Distillation of methylene chloride gave a pinksolid, and recrystallization from methanol gave a white crystal of thespiro-oxazine of the formula (G).

(4) Results of analysis

Elementary analysis values:

    ______________________________________                                        Found Value (%)  Calculated Value (%)                                         ______________________________________                                        C       78.8         78.3                                                     H       5.8          5.4                                                      N       7.2          7.6                                                      ______________________________________                                    

NMR: 1.4 ppm (6H), 2.8 ppm (3H), 6.6-8.5 ppm (11H)

Melting point: 158° C.

(5) Application

A coating solution was prepared by dissolving 0.1 g of the spiro-oxazineof the formula (G) in 100 g of a 10% solution of polyvinyl butyral inbutanol, and the coating solution was coated on two glass sheets. Thecoated glass sheets were dried and piled so that the resin-coatedsurfaces confronted each other, and the piled glass sheets were heated.

When the so-prepared photochromic laminated glass was irradiated withultraviolet rays, the laminated glass became green. If the light wasremoved and the laminated glass was allowed to stand in the dark, thelaminated glass became colorless again. When the laminated glass wasirradiated with light for 20 hours in a fade meter and the lightresistance was examined, it was found that the photochromiccharacteristics were the same as those before the placement in the fademeter, and it was confirmed that the fatigue resistance was excellent.When the absorption characteristics at the time of coloration inmethanol were examined, it was found that absorption peaks λ_(max)appeared at 460 nm and 632 nm.

EXAMPLE 2

(1) Synthesis of spiro-oxazine of following formula (S): ##STR14##

A white crystal of the spiro-oxazine of the formula (S) was obtained inthe same manner as described in Example 1 except that1,3,3-trimethyl-2-methylene-5,6-dichloroindoline was used instead of1,3,3-tri-methyl-2-methyleneindoline

(2) Results of analysis

Elementary analysis values:

    ______________________________________                                        Found Value (%)  Calculated Value (%)                                         ______________________________________                                        C       66.1         65.9                                                     H       3.8          4.1                                                      N       6.5          6.4                                                      ______________________________________                                    

Melting point: 204°-205° C. NMR: 1.5 ppm (6H), 2.8 ppm (3H), 6.4-8.4 ppm(9H)

(3) Application

A laminated glass was prepared in the same manner as described inExample 1 by using the so-obtained compound. When the laminated glasswas irradiated with ultraviolet rays, the laminated glass became green,and if the light was removed and the laminated glass was allowed tostand in the dark, the laminated glass became colorless again. When thelaminated glass was irradiated with light for 20 hours in a fade meterand the light resistance was examined, it was found that thephotochromic characteristics were the same as those before the placementin the fade meter and the light resistance was excellent.

EXAMPLE 3

(1) Synthesis of spiro-oxazine of formula (H) ##STR15##

In 100 ml of benzene were dissolved 10 g of 2,3,3-trimethylindolenineand 15 g of 2,3,4,5,6-pentamethylbenzyl chloride, and the solution wasrefluxed for 2 hours. Then, the temperature of the reaction liquid waslowered to about 50° C., and 3 g of triethylamine and 10 g of1-nitroso-2-hydroxydibenzofuran were added to the reaction liquid.Reaction was carried out at the reflux temperature for 1 hour. Then, thepurification was carried out in the same manner as described in Example1 to obtain a white crystal of the spiro-oxazine of the formula (G).

(2) Results of analysis

Elementary analysis values:

    ______________________________________                                        Found Value (%)  Calculated Value (%)                                         ______________________________________                                        C       81.9         81.7                                                     H       6.8          6.6                                                      N       5.2          5.4                                                      ______________________________________                                    

NMR: 1.4 ppm (6H), 2.2 ppm (15H), 4.3 ppm (2H), 6.4-8.5 ppm (11H)

(3) Application

A laminated glass was prepared in the same manner as described inExample 1 by using the so-prepared compound. When the absorptioncharacteristics of the laminated glass at the time of coloration wereexamined, it was found that the absorption peaks λ_(max) appeared at 460nm and 632 nm.

EXAMPLES 4 through 11

(1) The following compounds having substituents at the positions athrough g were prepared in the same manner as described in Example 3.##STR16##

The compound of Example 4 had Cl at each of the positions a, b, c and e.

The compound of Example 5 had F at each of the positions c, d, e, f andg.

The compound of Example 6 had OCH₃ at each of the positions a and c andNO₂ at the position e.

The compound of Example 7 had a methacryloxy group at the position a.

The compound of Example 8 had a methoxy group at the position a and avinyl group at the position e.

The compound of Example 9 had H at each of the positions a through g.

The compound of Example 10 had Cl at each of the positions c and e.

The compound of Example 11 had CH₃ at the position d.

(2) Results of analysis

Elementary analysis values:

    ______________________________________                                                 C (%)      H (%)   N (%)                                             ______________________________________                                        Example 4  62.2         3.5     4.7                                                      (61.9)       (3.4)   (4.8)                                         Example 5  67.5         3.9     5.0                                                      (67.4)       (3.6)   (5.2)                                         Example 6  70.3         5.2     7.6                                                      (69.9)       (4.9)   (7.7)                                         Example 7  77.1         5.2     5.3                                                      (77.3)       (5.3)   (5.3)                                         Example 8  79.0         5.3     5.7                                                      (79.2)       (5.6)   (5.6)                                         Example 9  81.1         5.3     6.3                                                      (81.1)       (5.4)   (6.3)                                         Example 10 70.2         4.0     5.5                                                      (70.2)       (4.3)   (5.5)                                         Example 11 81.0         5.8     6.0                                                      (81.2)       (5.7)   (6.1)                                         ______________________________________                                    

Each value is a found value but each of the parenthesized values is acalculated value.

NMR: Example 9: 1.4 ppm (6H), 4.4 ppm (4H), 6.3-8.4 ppm (16H) Example10: 1.4 ppm (6H), 4.5 ppm (2H), 6.3-8.4 ppm (14H) Example 11: 1.4 ppm(6H), 2.3 ppm (3H), 4.5 ppm (2H), 6.2-8.5 ppm Melting point: Example 9:157°-158° C. Example 10: 150° C.

(3) Application

Laminated glasses were prepared in the same manner as described inExample 1 by using the compounds of Examples 4 through 6. Each of thelaminated glasses became green under irradiation with ultraviolet rays.

In 20 g of toluene were dissolved 1 g of the compound of Example 7 and10 g of n-butyl methacrylate, and solution polymerization was carriedout by using azobisisobutyronitrile as the polymerization initiator.When the polymer solution was coated on a slide glass, a transparentcoating film was obtained. When the glass sheet was irradiated withultraviolet rays, the glass sheet became green, and when the light wasremoved and the glass sheet was allowed to stand in the dark, the glasssheet became colorless again.

A glass sheet was similarly prepared by using the compound of Example 8,and the glass sheet became green under irradiation ,with ultravioletrays.

A coating solution formed by dissolving 0.1 g of the compound of Example9 in a 10% solution of an acrylic polymer in toluene was coated on twoglass sheets. The glass sheets were dried and piled so that theresin-coated surfaces confronted each other, and the laminate thenheated.

When the so-prepared photochromic laminated glass was irradiated withultraviolet rays, the laminated glass became green, and when the lightwas removed and the laminated glass was allowed to stand in the dark,the laminated glass became colorless again. When the laminated glass wasirradiated with light for 20 hours in a fade meter and the lightresistance was examined, it was found that the photochromiccharacteristics were the same as those before the placement in the fademeter and the light resistance was excellent. When the absorptioncharacteristics at the time of coloration were examined, it was foundthat the absorption peaks λ_(max) appeared at 486 nm and 632 nm.

A laminated glass was prepared in the same manner as described above byusing the compound of Example 10, and when the absorptioncharacteristics at the time of coloration were examined, it was foundthat the absorption peaks λ_(max) appeared at 486 run and 628 nm.

A coating solution comprising 0.1 g of the compound of Example 11, 0.03g of a hindered amine type light stabilizer (LA-57 supplied byAdeca-Argus), 0.04 g of a hindered amine type light stabilizer (LA-77supplied by Adeca-Argus), 0.02 g of a hindered phenol type antioxidant(AO-60 supplied by Adeca-Argus), 0.01 g of di(2-ethylhexyl) adipate as aplasticizer, 0.1 g of dimethyl diphenate and 100 g of a 10% solution ofpolyvinyl butyral in butanol was coated on two glass sheets. The coatedglass sheets were dried and piled so that the resin-coated surfacesconfronted each other, and the laminate then heated. When theso-prepared photochromic laminated glass was irradiated with ultravioletrays, the laminated glass became green, and when the light was removedand the laminated glass was allowed to stand in the dark, the laminatedglass became colorless again. When the laminated glass was irradiatedwith light for 20 hours in a fade meter and the light resistance wasexamined, it was found that the light resistance was good.

EXAMPLE 12

(1) Synthesis of spiro-oxazine of following formula (I): ##STR17##

To a solution comprising 15 g of1-(6-hydroxy-hexyl)-2,3,3-trimethylindolenium iodide, 10 g oftriethylamine and 100 ml of methylene chloride was added dropwise 15 gof methacryloyl chloride. After the dropwise addition, the mixture wasstirred for 1 hour. Then, 100 ml of water was added to the mixture, andthe mixture was extracted with methylene chloride. The methylenechloride layer was concentrated to obtain 11 g of1-(6-methacryloxy)hexyl-2-methylene-3,3-dimethylindoline. The reactionwas carried out in the same manner as described in Example 1 except thatthe so-obtained compound was used instead of1,3,3-trimethyl-2-methylene-indoline, whereby a yellow liquid of thespiro-oxazine of the formula (I) was obtained.

(2) Results of analysis

Elementary analysis values:

    ______________________________________                                        Found Value (%)  Calculated Value (%)                                         ______________________________________                                        C       75.8         75.9                                                     H       6.4          6.5                                                      N       5.4          5.4                                                      ______________________________________                                    

IR: 1720 cm⁻¹

NMR: 1.2-2.0 ppm (17H), 3.2 ppm (2H), 4.1 ppm (2H), 5.5 ppm (1H), 6.1ppm (1H), 6.6-8.5 ppm (11H)

(3) Application

In the same manner as described in Example 7, a coated glass sheet wasprepared by using the spiro-oxazine of the formula (I). When the glasssheet was irradiated with ultraviolet rays, the glass sheet becamegreen, and when the light was removed and the glass sheet was allowed tostand in the dark, the glass sheet became colorless again. When theabsorption characteristics at the time of coloration were examined, itwas found that the absorption peaks λ_(max) appeared at 486 nm and 633nm.

When the glass sheet was subjected to the durability test where theglass sheet was irradiated with light for 20 hours in a fade meter, nosubstantial degradation was observed, and it was confirmed that theglass sheet had a good durability.

EXAMPLE 13

(1) Synthesis of spiro-oxazine compound of formula (J) ##STR18##

The above compound was synthesized in a manner similar to the manneradopted in Example 1.

(2) Results of analysis

Elementary analysis values:

    ______________________________________                                        Found Value (%)  Calculated Value (%)                                         ______________________________________                                        C       72.2         72.4                                                     H       5.4          5.3                                                      N       7.4          7.7                                                      ______________________________________                                    

IR: 3380 cm⁻¹ , 3340 cm⁻¹, 1710 cm⁻¹, 1540 cm⁻¹, 1250 cm⁻¹, 1025 cm⁻¹

(3) Application

The spiro-oxazine of the formula (J) was dissolved in methylmethacrylate at a concentration of 0.5% by weight, and castpolymerization was carried out by using azobisisobutyronitrile as thepolymerization initiator to obtain a polymethyl methacrylate sheet inwhich the compound of the formula (J) was incorporated.

When the sheet was irradiated with ultraviolet rays, the sheet becamegreen, and when the light was removed and the sheet was allowed to standin the dark, the sheet promptly became colorless again. When theabsorption characteristics at the time of coloration were examined, itwas found that the absorption peaks λ_(max) appeared at 490 nm and 706run. This sheet became green even at 50° C. under irradiation withultraviolet rays, and the coloration-possible temperature was higherthan 50° C.

EXAMPLE 14

(1) Synthesis of 2,3,3-trimethylbenz(g)indolenine

To 10 g of 1-naphthylhydrazine hydrochloride and 30 g of methylisopropyl ketone was added dropwise 5 g of sulfuric acid, and reactionwas carried out at the reflux temperature for 2 hours. The reactionmixture was neutralized with a 20% aqueous solution of sodium hydroxideand extracted with water/ether, and the ether layer was concentrated toobtain 8 g of 2,3,3trimethylbenz(g)indolenine.

(2) Synthesis of 1,2,3,3-tetramethylbenz(g)indolenium iodide

A solution comprising 8 g of 2,3,3-trimethylbenz(g)indolenine and 25 gof methyl iodide was reacted at the reflux temperature for 30 minutes.The formed precipitate was recovered by filtration and washed withacetone to obtain 12 g of a white crystal.

(3) Synthesis of spiro-oxazine of following formula (K): ##STR19##

A solution of 12 g of 1,2,3,3-tetramethylbenz(g)indolenium iodide and 10g of 1-nitroso-2-hydroxydibenzofuran in 50 ml of isopropanol was heatedto 50° C., and 5 g of piperidine was added to the solution. Then,reaction was carried out at the reflux temperature for 1 hour. Thereaction mixture was concentrated and subjected to the columnchromatography separation using silica gel as the supporting carrier andtoluene as the developing solvent. Distillation of the solvent gave apink solid. When this solid was recrystallized from butanol, a lightyellow crystal of the compound of the formula (K) was obtained.

(4) Results of analysis

Elementary analysis values:

    ______________________________________                                        Found Value (%)  Calculated Value (%)                                         ______________________________________                                        C       80.5         80.4                                                     H       5.6          5.3                                                      N       6.4          6.7                                                      ______________________________________                                    

NMR: 1.4 ppm (6H), 3.4 ppm (3H), 6.4-8.7 ppm (13H)

(5) Application

A laminated glass was prepared in the same manner as described inExample 9 by using the compound of the formula (K). When the laminatedglass was irradiated with ultraviolet rays, the laminated glass becamegreen, and when the light was removed and the laminated glass wasallowed to stand in the dark, the laminated glass-became colorlessagain. When the laminated glass was irradiated with light for 20 hoursin a fade meter and the light resistance was examined, it was found thatthe photochromic characteristics were the same as those before theplacement in the fade meter and the fatigue resistance was excellent.When the absorption characteristics at the time of coloration wereexamined, it was found that the absorption peaks λ_(max) appeared at 465nm and 650 run.

EXAMPLES 15 through 18

Compounds of the following formula having substituents at the positionsa and b were synthesized in a manner similar to the manner adopted inExample 7: ##STR20##

The compound of Example 15 had ##STR21## at the position a.

The compound of Example 16 had --CH₃ at the position a and --CO₂ H atthe position b.

The compound of Example 17 had --CH₃ at the position a and --CH₂ OH atthe position b.

The compound of Example 18 had ##STR22## at the position a and ##STR23##at the position b. (2) Results of analysis

Elementary analysis values:

    ______________________________________                                                 C (%)      H (%)   N (%)                                             ______________________________________                                        Example 15 82.9         5.3     5.4                                                      (82.7)       (5.5)   (5.5)                                         Example 16 75.3         4.7     6.0                                                      (75.3)       (4.8)   (6.1)                                         Example 17 77.4         5.3     6.2                                                      (77.7)       (5.4)   (6.3)                                         Example 18 75.2         5.2     4.7                                                      (75.3)       (5.4)   (5.0)                                         ______________________________________                                    

Each value is a found value, but each of the parenthesized values is acalculated value.

Laminated glasses were prepared in the same manner as described inExample 9 by using the compounds of Examples 15 through 17. Each of thelaminated glasses became green under irradiation with ultraviolet rays.

A glass sheet was prepared in the same manner as described in Example 7by using the compound of Example 18. The glass sheet became green underirradiation with ultraviolet rays.

EXAMPLE 19

(1) Synthesis of 2,3,3-trimethylbenz(f)indolenine

Reaction was carried out in the same manner as described in (1) ofExample 14 except that 2-naphthylhydrazine hydrochloride was usedinstead of 1-naphthylhydrazine hydrochloride

(2) Synthesis of spiro-oxazine of following formula (L): ##STR24##

In 40 ml of ethanol were dissolved 6 g of the compound prepared in (1)above and 10 g of methyl tosylate, and reaction was carried out at thereflux temperature for 2 hours. The temperature of the reaction liquidwas lowered to 50° C., and 2 g of triethylamine and 10 g of1-nitroso-2-hydroxy-8-bromodibenzofuran were added to the reactionliquid. Reaction was carried out at the reflux temperature for 2 hours,and the subsequent procedures were the same as described in Example 1and a light yellow crystal of the compound of the formula (L) wasobtained.

(3) Results of analysis

Elementary analysis values:

    ______________________________________                                        Found Value (%)  Calculated Value (%)                                         ______________________________________                                        C       67.3         67.6                                                     H       4.0          4.2                                                      N       5.7          5.6                                                      ______________________________________                                    

EXAMPLE 20

(1) Synthesis of 4,4-dimethyl-5-oxohexane-nitrile

A mixture of 40 g of 3-methyl-2-butanone and 2 g of Triton B was heatedto 350° C., and 20 g of acrylonitrile was added to the mixture over aperiod of 1 hour. Then, the mixture was stirred for 18 hours, andhydrochloric acid was added to the mixture to make the mixture acidicand the mixture was extracted with ether.

(2) Synthesis of compound of following formula (VI): ##STR25##

A mixture of 50 g of 4,4-dimethyl-5-oxo-hexane-nitrile, 6 g of ethyleneglycol, 30 ml of petroleum ether and 0.3 g of p-toluenesulfonic acidmonohydrate was reacted at the reflux temperature for hours, and thereaction liquid was concentrated.

(3) Synthesis of compound of following formula (VII): ##STR26##

A solution of 20 g of the compound of the formula (VI) in 200 ml ofether was added dropwise to 20 g of lithium aluminum hydride and 300 mlof ether over a period of 30 minutes, and reaction was carried out atthe reflux temperature for 2 hours and the reaction liquid was cooled.Water was added to the reaction liquid to decompose the excess oflithium aluminum hydride. The reaction mixture was filtered, and thefiltrate was concentrated.

(4) Synthesis of 2,3,3-trimethyl-3,4,5,6-tetrahydropyridine

To a solution of 20 g of the compound of the formula (VII) in 50 ml ofethanol was added 110 ml of 1N hydrochloric acid, and the mixture washeated and refluxed for 1 hour. Then, the reaction mixture wasconcentrated.

(5) Synthesis of 1,3,3-trimethyl-2-methylenepiperidine

A mixture of 5 g of 2,3,3-trimethyl-3,4,5,6-tetrahydropyridine and 12 gof methyl tosylate was reacted at 100° C. for 4 hours. The reactionmixture was cooled and extracted with water/chloroform. Then, 2 g ofsodium hydroxide was added to the water layer and the mixture wasstirred. The liquid was extracted with chloroform. The chloroform layerwas concentrated to obtain a yellow liquid.

(6) Synthesis of spiro-oxazine of following formula (M): ##STR27##

A milky white crystal of the compound of the formula (M) was prepared inthe same manner as described in Example 1 except that1,3,3-trimethyl-2-methylenepiperidine was used instead of1,3,3-trimethyl-2-methylene-indoline.

(7) Results of Analysis

Elementary analysis values:

    ______________________________________                                        Found Value (%)  Calculated Value (%)                                         ______________________________________                                        C       75.5         75.5                                                     H       6.6          6.6                                                      N       8.4          8.4                                                      ______________________________________                                    

EXAMPLE 21

(1) Synthesis of spiro-oxazine of following formula (N): ##STR28##

A white crystal of the spiro-oxazine of the formula (N) was prepared inthe same manner as described in Example 1 except that1-nitroso-2-hydroxy-3-methacryloxymethyldibenzofuran was used instead of1-nitroso-2-hydroxydibenzofuran.

(2) Results of analysis

Elementary analysis values:

    ______________________________________                                        Found Value (%)  Calculated Value (%)                                         ______________________________________                                        C       74.4         74.7                                                     H       5.5          5.6                                                      N       6.1          6.0                                                      ______________________________________                                    

IR: 1720 cm⁻¹

(3) Application

A glass sheet was prepared in the same manner as described in Example 7by using the compound of the formula (N). When the glass sheet wasirradiated with ultraviolet rays, the glass sheet became green, and whenthe light was removed and the glass sheet was allowed to stand in thedark, the glass sheet became colorless again.

EXAMPLE 22

(1) Synthesis of spiro-oxazine of following formula (O): ##STR29##

A solution comprising 15 g of1-nitroso-2-hydroxy-8-(N-methacryloxyethyl)carbamoyloxydibenzothiophene,20 g of piperidine and 100 ml of trichloroethylene was heated to thereflux temperature. Then, 9 g of1,3-dimethyl-3-ethyl-2-methylene-indoline was added dropwise to thesolution being refluxed over a period of 30 minutes. After the dropwiseaddition, reaction was carried out at the reflux temperature for 2hours. After the reaction, the purification was carried out in the samemanner as described in Example 1 to obtain a white crystal of thespiro-oxazine of the formula (O).

(2) Results of analysis

Elementary analysis values:

    ______________________________________                                        Found Value (%)  Calculated Value (%)                                         ______________________________________                                        C       68.1         68.1                                                     H       6.2          6.1                                                      N       8.5          8.6                                                      S       4.6          4.9                                                      ______________________________________                                    

IR: 3330 cm⁻¹, 1740 cm⁻¹, 1717 cm⁻¹, 1680 cm⁻¹, 1540 cm⁻¹

(3) Application

When a solution of the compound of the formula (O) in acetone wasirradiated with ultraviolet rays, the solution became red, and when thelight was removed and the solution was allowed to stand in the dark, thesolution became colorless. Even when the above procedure was repeated 10times, the photochromic characteristics were not changed at all.

EXAMPLE 23

Synthesis of spiro-oxazine of following formula (P): ##STR30##

A milky white crystal of the spiro-oxazine of the formula (P) wasobtained in Example 1 except that1-methyl-3-spirocyclohexyl-2-methylene-indoline was used instead of1,3,3-trimethyl-2-methylene-indoline and3-hydroxy-4-nitroso-9-(4-vinyl)benzylcarbazole was used instead of1-nitroso-2-hydroxydibenzofuran.

(2) Results of analysis

Elementary analysis values:

    ______________________________________                                        Found Value (%)  Calculated Value (%)                                         ______________________________________                                        C       82.5         82.6                                                     H       6.0          6.3                                                      N       7.9          8.0                                                      ______________________________________                                    

(3) Application

When a solution of the compound of Example 23 in acetone was irradiatedwith ultraviolet rays, the solution became red, and when the light wasremoved and the solution was allowed to stand in the dark, the solutionbecame colorless again. Even when the above procedure was repeated 10times, the photochromic characteristics were not changed at all.

EXAMPLE 24

(1) Synthesis of spiro-oxazine of following formula (Q): ##STR31##

A light yellow crystal of the compound of the formula (Q) was obtainedin the same manner as described in Example 1 except that1,3,3-trimethyl-2-methylene-5-acrylaminoindoline was used instead of1,3,3-tri-methyl-2-methylene-indoline and8-hydroxy-9-nitroso(-1,2-benzodiphenylene oxide) was used instead of1-nitroso-2-hydroxydibenzofuran.

(2) Results of analysis

Elementary analysis values:

    ______________________________________                                        Found Value (%)  Calculated Value (%)                                         ______________________________________                                        C       76.2         76.4                                                     H       4.8          5.1                                                      N       8.8          8.6                                                      ______________________________________                                    

IR: 1675 cm⁻¹

(3) Application

When a solution of the compound of the formula (Q) in acetone wasirradiated with ultraviolet rays, the solution became green, and whenthe light was removed and the solution allowed to stand in the dark, thesolution became colorless. Even when the above procedure was repeated 10times, the photochromic characteristics were not changed at all.

EXAMPLE 25

(1) Synthesis of 2-hydroxy-9-methylcarbazole

To a mixture comprising 20 g of 2-hydroxycarbazole, 3 g ofbenzyltriethyl ammonium chloride, 70 ml of a 50% aqueous solution ofsodium hydroxide and 10 ml of benzene was added dropwise 25 g of methyliodide. After the dropwise addition, the mixture was stirred for 2hours. The mixture was poured into hot water and the mixture was allowedto stand at room temperature overnight. The precipitated solid wasrecovered by filtration, washed with water and dried to obtain ayellowish brown solid of 2-hydroxy-9-methylcarbazole.

(2) Synthesis of 1-nitroso-2-hydroxy-9-methylcarbazole

A red solid of 1-nitroso-2-hydroxy-9-methylcarbazole was prepared in thesame manner as described in (1) of Example 1 except that the compoundobtained in (1) above was used instead of 2-hydroxydibenzofuran.

(3) Synthesis of spiro-oxazine of following formula (R): ##STR32##

A greenish white crystal of the spiro-oxazine of the formula (R) wasprepared in the same manner as described in (2) of Example 1 except thatthe compound obtained in (2) above was used instead of1-nitroso-2-hydroxydibenzofuran.

(4) Results of analysis of compound of formula (R)

Elementary analysis values:

    ______________________________________                                        Found Value (%)  Calculated Value (%)                                         ______________________________________                                        C       78.7         78.7                                                     H       5.9          6.0                                                      N       10.8         11.0                                                     ______________________________________                                    

(5) Application

When a solution of the compound of the formula (R) in acetone wasirradiated with ultraviolet rays, the solution became red, and when thelight was removed and the solution was allowed to stand in the dark, thesolution became colorless. Even when the above procedure was repeated 10times, the photochromic characteristics were not changed at all.

INDUSTRIAL APPLICABILITY

Since the spiro-oxazine compound of the present invention has connectedbenzene, heterocyclic 5-membered and benzene (or naphthalene) rings,represented by a dibenzofuran ring, the spiro-oxazine compound of thepresent invention has absorption peaks in both the short wavelengthregion (less than 550 nm) having a yellow chromophoric seed and the longwavelength region (larger than 600 run) having a blue chromophoric seedin the visible ray region. Accordingly, a green chromophoric seed notobtainable by the conventional technique can be realized, and anabundance of hues can be selected. Therefore, the spiro-oxazine compoundof the present invention is an epoch-making photochromic compound.Furthermore, the fatigue resistance is good.

Accordingly, the compound of the present invention is valuable as anoptical element such as sunglasses, ski goggles or protective glasslens, or a material for curtaining, clothing, automobile windows, toys,writing tools, or rewritable optical disks.

We claim:
 1. A spiro-oxazine compound represented by the followingformula (B) or (B'): ##STR33## wherein R⁰ is a substituent selected fromthe group consisting of an alkyl group having 1 to 20 carbon atoms, analkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to20 carbon atoms and an aryl group having 6 to 19 carbon atoms; x isselected from the group consisting of O, S, Se and N--R¹ wherein R¹ isselected from the group consisting of a hydrogen atom, an alkyl grouphaving 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbonatoms, an aralkyl group having 7 to 20 carbon atoms, an aryl grouphaving 6 to 19 carbon atoms and an acyl group having 2 to 20 carbonatoms; R² and R³ are a substituent selected from the group consisting ofa hydrogen atom, a hydroxyl group, an amino group having 0 to 20 carbonatoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy grouphaving 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbonatoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy grouphaving 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms,an alkenyl group having 2 to 20 carbon atoms, an arlkyl group having 7to 5 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogengroup, a cyano group, a carboxyl group, a nitro group, an acyl grouphaving 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, acarbamoyl group having 2 to 20 carbon atoms, and sulfonic acid group,with the proviso that R² is not a hydrogen atom and R³ is not a nitrogroup; k is an integer of from 0 to 2; R⁴ and R⁵ independently stand fora substituent selected from the group consisting of an alkyl grouphaving 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbonatoms and an aryl group having 6 to 19 carbon atoms, or R⁴ and R⁵together form a cycloalkyl group having 3 to 10 carbon atoms with thecarbon atoms at the 3'-position, R⁶ and R⁷ stand for a substituentselected from the group consisting of a hydroxyl group, an amino group,an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, anacyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkylgroup having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbonatoms, a halogen group, a cyano group, a carboxyl group, a nitro group,an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl grouphaving 2 to 20 carbon atoms, a carbamoyl group, a carbamoyloxy group anda sulfonic acid group, and l and m stand for an integer of from 0 to 4.2. A spiro-oxazine compound represented by the following formula (C) or(C'): ##STR34## wherein R⁰, R², R³, X and k are as defined in claim 1,R⁴ and R⁵ independently are selected from the group consisting of analkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20carbon atoms and an aryl group having 6 to 19 carbon atoms, or R⁴ and R⁵together form a cycloalkyl group having 3 to 10 carbon atoms with thecarbon atoms at the 3'-position, R⁶ and R⁷ are selected from the groupconsisting of a hydroxyl group, an amino group having 0 to 20 carbonatoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy grouphaving 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbonatoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl grouphaving 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbonatoms, an aralkyl group having 7 to 15 carbon atoms, an aryl grouphaving 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxylgroup, a nitro group, an acyl group having 2 to 20 carbon atoms, analkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl grouphaving 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbonatoms and a sulfonic acid group, and l and m are an integer of from 0 to4, R⁸ is selected from the group consisting of a hydroxyl group, anamino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxygroup having 6 to 14 carbon atoms, an acyloxy group having 2 to 20carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenylgroup having 2 to 20 carbon atoms, an aralkyl group having 7 to 15carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogengroup, a cyano group, a carboxyl group, a nitro group, an acyl grouphaving 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, acarbamoyloxy group having 2 to 20 carbon atoms and a sulfonic acidgroup, and n is an integer of from 0 to
 2. 3. A spiro-oxazine compoundrepresented by the following general formula (D) or (D'): ##STR35##wherein R⁰, R², R³, and x and k are as defined in claim 1, R⁴ and R⁵independently are selected from the group consisting of an alkyl grouphaving 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbonatoms and an aryl group having6 to 19 carbon atoms, or R⁴ and R⁵together form a cycloalkyl group having 3 to 10 carbon atoms with thecarbon atoms at the 3'-position, R⁶ and R⁷ are selected from the groupconsisting of a hydroxyl group, an amino group having 0 to 20 carbonatoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy grouphaving 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbonatoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl grouphaving 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbonatoms, an aralkyl group having 7 to 15 carbon atoms, an aryl grouphaving 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxylgroup, a nitro group, an acyl group having 2 to 20 carbon atoms, analkoxycarbonyl group having2 to 20 carbon atoms, a carbamoyl grouphaving 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbonatoms and a sulfonic acid group, and l and m are an integer of from 0 to4, R⁸ is selected from the group consisting of a hydroxyl group, anamino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxygroup having 6 to 14 carbon atoms, an acyloxy group having 2 to 20carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenylgroup having 2 to 20 carbon atoms, an aralkyl group having 7 to 15carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogengroup, a cyano group, a carboxyl group, a nitro group, an acyl grouphaving2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, acarbamoyloxy group having 2 to 20 carbon atoms and a sulfonic acidgroup, and n is an integer of from 0 to
 2. 4. A spiro-oxazine compoundrepresented by the following formula (E), or (E'): ##STR36## wherein R⁰,R², R³, X and k are as defined in claim 1, R⁴ and R⁵ independently areselected from the group consisting of an alkyl group having 1 to 20carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an arylgroup having 6 to 19 carbon atoms, or R⁴ and R⁵ together form acycloalkyl group having 3 to 10 carbon atoms with the carbon atoms atthe 3'-position, R⁶ and R⁷ are selected from the group consisting of ahydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxygroup having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxygroup having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbonatoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl grouphaving 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms,a halogen group, a cyano group, a carboxyl group, a nitro group, an acylgroup having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, acarbamoyloxy group having 2 to 20 carbon atoms and a sulfonic acidgroup, and l and m are an integer of from 0 to 4, and R⁹, R¹⁰, R¹¹, R¹²,R¹³, and R¹⁴ are selected from the group consisting of a hydrogen atom,an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to20 carbon atoms and an aryl group having 6 to 19 carbon atoms.
 5. Aspiro-oxazine compound represented by the following formula (F) or (F'):##STR37## wherein R⁰, R², R³, X and k are as defined in claim 1, R⁴ andR⁵ independently are selected from the group consisting of an alkylgroup having 1 to 20 carbon atoms, an aralkyl group having 7 to 20carbon atoms and an aryl group having 6 to 19 carbon atoms, or R⁴ and R⁵together form a cycloalkyl group having 3 to 10 carbon atoms with thecarbon atoms at the 3'-position, R⁶ and R⁷ stand for a substituentselected from the group consisting of a hydroxyl group, an amino grouphaving 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbonatoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy grouphaving 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbonatoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl grouphaving 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbonatoms, an aryl group having 6 to 14 carbon atoms, a halogen group, acyano group, a carboxyl group, a nitro group, an acyl group having 2 to20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, acarbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having2 to 20 carbon atoms and a sulfonic acid group, and l and m are aninteger of from 0 to 4, R¹⁵ is selected from the group consisting of ahydroxyl group, an amino group, an alkoxy group having 1 to 20 carbonatoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy grouphaving 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbonatoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl grouphaving 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbonatoms, an aryl group having 6 to 14 carbon atoms, a halogen group, acyano group, a carboxyl group, a nitro group, an alkoxycarbonyl grouphaving 2 to 20 carbon atoms, a carbamoyl group, a carbamoyloxy group anda sulfonic acid group, and t is an integer of from 0 to 2.